Copperable polyazo dyestuffs



United States Patent "ce 2,727,887

Patented Dec. 20, 1955 1 mol of diazotised Z-amino-l-hydroxybenzenet-methyl 2,727,887 sulphone can be coupled with 1 mol of 2-(4-aminobenzoylamino)--hydroxynaphthalene-7-sulphonic acid to COPPERABLE POLYAZO DYESTUFFS form the amino monoazo dyestufif and finally this may 5 be treated with phosgene. ig g ii g g figi fifggg ggg :3 1 In the form of their easily soluble alkali salts the poly- Switzerland, Swi fi azo dyestuffs according to the present invention are dark powders which dissolve in water with a violet colour No Drawing fapphcatlon April 10,1952 and in concentrated sulphuric acid with a red colour. Sena] 281683 They are distinguished by a very good aifinity to cellu- Claims priority, application Switzerland April 23, 1951 lose fibres and dye such fibres in pure bluish-red shades from a bath containing Glaubers salt according to the 3 Clalms- (CL 260-173) usual method. The bath is exhausted to a great extent.

Very good light, perspirationand wet-fastness dyeings The present process concerns the production of polyazo can be fixed by a treatment with agents yielding copper. dyestuffs, the cellulose dyeings of which have very pure The direct cellulose dyeings can be coppered either bluish-red shades, have very good fastness to light and in the dye bath or in a fresh bath with the usual copper extraordinarily good wet fastness properties. They are salts, e. g. copper acetate or copper sulphate, in a neutral a valuable addition to the range of direct drawing azo to weakly acid aqueous solution. If desired, copper comdyestuffs for cellulose fibres which can be fixed fast to pounds which are stable to alkalies may be used such light and wetness by coppering. as are obtained for example by reacting copper sulphate The polyazo dyestuifs according to the present invenwith sodium tartrate in a soda alkaline bath.

tion are obtained by coupling 2 mols of diazotised 2- The following examples illustrate the invention. Where amino-l-hydroxybenzene-4-methyl sulphone with 1 mol not otherwise stated, parts are given as parts by weight ofacoupling component of the general formula: and the temperatures are in degrees centigrade. The

I nofimma-o oGx-Oo o-NH 303E wherein X represents an azo, azoxy or urea linkage. relationship of parts by weight to parts by volume is The new polyazo dyestufis correspond to the formula that of kilogrammes to litres.

03 11 (In: OH

N=N N=N H038 NH-CO-OXOCO-NH soar OgCH; AOQCH: wherein X has the aforesaid significance. Example 1 h ebupllllg eompehehts usable aeebfdhlg t0 the P 18.7 parts of 2 amino-1-hydroxybenzene-4-methyl suleht Invention are Obtalned from b y 5 phone are dissolved in 200 parts of water with the addiy {y P Ph aeltt either y tion of 15 parts of concentrated hydrochloric acid and duclhg the nltro group to the p y amino g p and diazotised at 10 with 6.9 parts of sodium nitrate. The

treating the t compound With Phosgene 50 that 2 suspension obtained is poured at into a solution of molecules are l e y a F linkage, of y can be 38.8 parts of 2-(4'-nitrobenzoylamino)-5-hydroxynaphbbtallled by feduemg the 111tl'0 group in an alkaline thalene-7-sulphonic acid in 1500 parts of water, 3.6 parts dltlm, t glucose whereby two molecules are joined of sodium hydroxide and 4 parts of soda. As soon as y the formation e aZOXy 3Z0 linkage the coupling is complete, the monoazo dyestufi which Also, h following modifications 0f the Process Come has crystallised into fine small needles is filtered ofi. The t conslderatwn r e Production of the y fi dyestufi is dissolved at in 1000 parts of Water and accol'dlhg t e Present 1I1VeI1t10111 the coupling of 55 4.1 parts of sodium hydroxide. 32 parts of sodium hymol of drazotised Z-ammo-1-hydroxybenzenedroxide and 17.3 parts of glucose are added and the Sulphohe Wlth 1 11101 of y y' whole is kept for an hour at this temperature while stir droxyhaphthalehe-7-su-lphbnie acid to form the nitro ring. parts of common salt are then added and monoazo dyestufi and reduction of the nitro group, either the dyestuff which precipitates in the form of bronzem an alkaline medium with glucose so that two dyestufi 50 shimmering longish little needles is filtered off. It cormolecules are joined by the azo or 'azoxy group or by responds to the formula one of the usual methods, to the primary amino group The side products resulting from the reduction are washed and finally linking 2 molecules of the aminomonoazo away with a warm 5% common salt solution. When dyestufi with phosgene to form the urea derivative. Also dry, the dyestuff is in the form of a dark powder which 2,727,887 3 4 dissolves in water with the addition of soda with a violet common salt solution to remove the impurities. When colour and in concentrated sulphuric acid with a red dry, the dyestufi, which corresponds to the formula SIOQCH3 5020B; colour. It draws very Well on to natural or regenerated is a dark powder which dissolves in water with aviolet cellulose fibres. After treating with copper salts accordand in concentrated sulphuric acid with a red colour. ing to the usual methods, pure bluish-red shades are ob- It dyes cellulose fibres in bluish red shades which become tained which have excellent fastness to washing and light. still purer after treatment Wlth copper salts. The dyeings have very good lightperspirationand wet-fastness Example 2 properties.

The same dyestufi with the same fastness properties can be obtained if the diazonium compound obtained from 18.7 parts of Z-amino-l-hydroxybenzene-4-methyl sulphone is coupled with 35.8 parts of 2-(4'-aminobenzoylamino)-5-hydroxynaphthalene-7-sulphonic acid and the monoazo dyestufr" so obtained is treated with phosgene in a weakly alkaline solution until a sample canv no longer be diazotised and then worked up as described above.

38.8 parts of 2-(4-nitrobenzoylamino)-5-hydroxynaph- 15 thalene-7-sulphonic acid are dissolved in 200 parts of water and 4.0 parts of sodium hydroxide at 40 and 16 parts of sodium hydroxide and. 17.3 parts of glucose are added. The whole is stirred for some hours at this temperature, 50 parts of common salt and parts of cone. hydrochloric acid are added, the monoazo dyestutf formed is filtered off and washed free of side products with 10% common'salt solution. The monoazo dyestufi E l 4 is dissolved in 1500 parts of water and 3.6 parts of soxamp e dium hydroxide at 40. 40 parts of soda are added to 25 1 P Of the dyestuff Obtained acwldmg to the Solution f the monoazo dyesmfi and then ths l is dissolved in a dyebath containing 3000 parts of water pension of the diazo compound produced according to and 2 Parts of Soda; 100 Parts of comm} f emerfid Example 1 from 18.7 parts of Z-amino-l-hydroxybenat 4050c: the bath heated to Wnhm zene-4-methyl sulphone is added to the monoazo dye- Pies, 30 Parts Of OdI m sulphate are added and dyeing stuff solution. When the coupling is complete, 8 parts 30 1S performFd for 45 Inmates at thls temperature The of sodium hydroxide and 250 parts of common salt are dye bath 1s nearly completely exhausted at the end of added, the trisazo dyestutf is filtered off and washed with T dyed goods are i cold and tfreated 10% common salt solution. The dyestufi has the same mmues m a fresh .bath comalnmg zparts o crystallised copper sulphate m 2000 parts of water and 2 Propel-figs as that descnbedmExamp 1e parts of acetic acid. The goods are rinsed and Example3 dried in the usual way. The cotton is dyed in pure bluish-red shades which have very good washing-, water-, Phosgene is introduced mto a 40 warm solution of perspiration. d1ight f t e Properties. 35.8 parts of 2-(4'-aminobenzoylamino)-5-hydroxynaph- Wh t w claim i thalene-7-sulphonic acid in 700 parts of water and 5 40 1. A polyazo dyestufi having the general formula:

OH OH OH OH I l l l =N- N=N H038 NH-C oQxQ-o o-Nn --so 311 502C113 S O2CHs parts of sodium hydroxide until a. sample can no longer wherein X represents a member selected from the group be diazotised. At the same time, a 20% soda solution consisting of N=N, and --NH-CO-NH- is added dropwise so that there is.v always a very slight 2'. Apolyazo dyestuii having the formula:

OH 311 1 (In; 0H

N=N '.-N=N 1105s NBC-SOON: Q-oo-NH soni Solon. 02cm acid reaction to litmus. The whole is heated to 3. Apolyazo dyestufi having the formula:

on 0H (3H C H N=N v -N=l l' Hots NH-C Q-O-Nrt-Q Q-NrL-O-C O-NH son; l SOQCH; 502011: 5% by volume of common salt is added and the urea References Cited inthe file of this patent WhICh precipitates 1S filtered off. The urea is dissolved UNITED STATES PATENTS in 1000 parts of water and 6 parts of sodium hydroxide and then 12.5 parts of sodium bicarbonate and the di- 1558890 Kahscher 1925 azonium compound obtained a ordi t E k 1 2,228,289 Q et a1 i 1941 from 18.7 parts of Z-arnino-1-hydr xyben en -4- ethy1 2341791 Kalser 1944 sulphone is added. The next day, the suspension is heated OTHER REFERENCES to 95, 4%- by volume of common salt is added and Georgievics et al.: Dye Chemistry (1920), pp. 4 and the dyestuff is filtered off and washed with a hot 3% 85. 

1. A POLYAZO DYESTUFF HAVING THE GENERAL FORMULA: 